Acrylic esters of glycol monoethers



Patented Mar. 12, 1946 .UNl'l-ED STATES-PATENT OFFICE I v 2,896,434

' ACRYLIClS'1121131 18 afialgliYO0LfldONiJ- Chessie E. Behberg, Glenside, and Charles H. Fisher, Abington, Pa., assignors to the United States of America, as represented by the Secretary of Agriculture No Drawing. Application duly 19, Serial N 3 Claims. (01. 260-488) (Granted under the act of 30, 1928;

, amended April This application is made under the act or March 3, 1883, as amended by the act of April' mono or poly glycol mono-ethers and to their production.

The alcoholysis process of preparing esters, in which an alcohol is reacted with an ester and the ester groups are interchanged, has long been known. However, in so far as known to us, this process has not previously been applied to the production of acrylic esters of glycol mono-ethers, probably because such acrylic esters polymerize very readily, and also the ether-alcohol used for the alcoholysis might be subject to cleavage in the presence of certain ester interchange catalysts.

March 3, 1883, as 370 0. G. 757) When no more methanol was obtained, the excess methyl acrylate was distilled off and the remaining :product was identified as beta.-

methoxyethyl acrylate (CHrlCHCOOCHsCHsOCHa), a liquid boiling at 56v C. at 12 mm. pressure. It had a refractive index, [n] of 1.4272, and a density, [1113. of 1.0131. The yield was 1.4 percent.

The acrylate thus obtained polymerized very readily when warmed with a little organic per- In accord with this invention, valuable acrylic esters, which are useful as derived and more useful when polymerized, have been prepared. These esters may generally be described as the acrylic esters of glycols wherein one of the hydroxyls of the glycol is esterifled with acrylic acid and the other is etherifled. These esters include methoxyethyl, ethoxyethyl, butoxyethyl, phenoxyethyl, benzyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, butoxyethoxyethyl, phenoxyethoxyethyl and similar beta-alkoxyand.

beta-aryloxyethyl and beta-alkoxyethoxyand beta-aryloxyethoxyethyl acrylates, having in general the formula radical. The following examples are given to illustrate the invention:

Exams: I

Two moles (152 g.) of beta-methoxyethanol,

6.0 moles (516 g.) of methyl acrylate, 5 g. oi hydroquinone, 1 g. of copper powder and 3 g. of p-toluenesulionic acid weremixed and refluxed in a flask attached to a rractionating column.

' tillate consisted of the azeotr'ope 01' methanol and methyl acrylate.

oxide,.the polymer being tough but elastic and rubberlike. It had less tack than an alkyl acrylate polymer of similar consistency and also had much better resistance to aliphatic hydrocarbons than did the latter. 1

Table I lists the physical properties of examples of the other glycol-ether acrylates which have been prepared bysubstantially the same procedure as described above. v

. Table 1 ram Yield E PM 8." a "W0. d- Per cent He ga ethoxyetbyl scry- 78 23 m y 1. Beta butoxyethyl acry- Y Y 9813 99 80 6 1.4310 91 lleta-ilgthylheroxyethyl 8 5 1 94 go scry 7 0. .4408 .9215 Betaphenoxyethyl scryo3 6 L 1 0. 5198 1.1 3 Beta-benzyloxyethyl 0 5 acryla 107 0. 7 1. 5075 l. 0741 68 Bota-methoxyethoxyethyl mime--. 117 21 1.4392 1. 0421 61 Betsethoryethoxyethyl acry to 4.8 1.4401 1.0m 67 Beta-butoryethoxyetbyi acrylate 77 0. 5 l. 4398' 9821 81 Bets-Z-ethylbexoryethoxyethyl scrylate..,..-.. 126 0. 4 1. 4510 9685 Betshenoxyethoxyetliy acrylste 2.2 1.5108 1.1103 88 wise, other polymerization inhibitors might be used, such as phenols, aryl amines, copper salts,

sulfur, and so forth. .Also, other means might be employedto remove the alcohol liberated in the reactio Thus, instead oi distilling the aseotrope oi the lower alkyl acrylic ester with the liberated alcohol, other entraining agents might be added to the reaction mixture to remove the al hol as its azeotropic mixture, suitable entrai g agents being aliphatic or aromatic hydrocarbons or chlorinated hydrocarbons of suitable boiling point. Furthermore, instead of using methyl acrylate as the lower alkyl acrylic ester, other esters such as ethyl or propyl acrylate might be used. The only limitation in the latter choice is the requirement that the ester used as a reagent must have a lower boiling point than that which is to be prepared.

The acrylic esters of the glycol mono-ethers prepared in accord with this invention can be polymerized very readily by known methods such as by action of heat, light, ozone, peroxides, and so forth, and the polymerization may be carried out in mass, in aqueous emulsion or in a suitable solvent. The polymers, in general, are soft, elastic, rubbery, and notably less tacky than those 20 prepared from alkyl acrylate monomers of comparable molecular weight. Another important advantage of the polymers of the glycol monoether acrylates over those of the alkyl acrylates is their much greater resistance to gasoline and other petroleum products. In addition to being polymerized alone, the products of this invention can be copolymerized with other polymerizable compounds of the acrylic or vinyl type to produce valuable products.

Having thus described the invention, what is claimed is:

1. An ester selected from the group consisting of beta-phenoxyethyl acrylate and beta-benzyloxyethyl acrylate.

2. Beta-phenoxyethyl acrylate.

3. Beta-benzyloxyethyl acrylate.

CHESSIE E. REHBERG. CHARLES H. FISHER. 

